Water-insoluble phenyl azo phenyl dyes



United States Patent Oifice 3,428,622 Patented Feb. 18, 1969 US. Cl. 260-207 12 Claims Int. Cl. C09b 29/12; D06p I/02 ABSTRACT OF THE DISCLOSURE Water-insoluble 2,4 dinitro-6-alkylsulfonylphenyl-azo- 3'-alkoxy-4'-(N-alkyl-N-acyloxy-, alkoxycarbonylor alkoxycarbonyloXy-alkylamino)benzenes, substituted in the 5'-position with either alkyl, alkoxy, acylamino, alkoxycarbonylamino, aralkoxycarbonylamino or aryloxycarbonylamino, are disperse dyes.

This invention relates to new dyes Which are virtually insoluble in water and are of the formula where R is a member selected from the group consisting of unsubstituted and halogen-, cyanoand hydroxy-substituted methyl and ethyl,

R stands for methoxy or ethoxy,

R stands for methyl, ethyl, propyl or butyl,

R is a member selected from the group consisting of unsubstituted and halogeno-, cyano-, alkoxyor acyl-substituted acyloxyalkyl, alkoxycarbonylalkyl and alkoxycarbonyloxyalkyl; and

R is a member selected from the group consisting of alkyl and alkoxy, unsubstituted and halogeno-, alkoxyor aryloxy-substituted acylamino, alkoxycarbonylamino, aralkoxycarbonylamino and aryloxycarbonylamino.

The process of their production consists of coupling a diazotized amine of formula IFIOz O2N NH2 302R: (II) with a compound of formula I R4 R5 (III) Especially preferred dyestuffs are of the formula I /Rs I R SO2R0 R10 (1 V where R is a member selected from the group consisting of unsubstituted and chlor0-, bromoor cyano-substituted methyl, unsubstituted and hydroxy-substituted ethyl,

R stands for methoxy or ethoxy,

R stands for methyl, ethyl, propyl or butyl,

R is a member selected from the group consisting of acetoxyethyl, chloroacetox'yethyl, ethoxyacetoxyethyl, propyloxyacetoxyethyl, butoxyacetoxyethyl, acetoxyacetoxy ethyl, propionylacetoxyethyl, butyrylacetoxyethyl, propionyloxyethyl, methoxycarbonylethyl, chloromethoxycarbonylethyl, methoxymethoxycar bonylethyl, ethoxycarbonylethyl, methoxyethoxycarbonylethyl, propyloxycarbonylethyl, methoxycarbonyloxyethyl, ethoxycarbonyloxyethyl, (Z-methoxypropyl)-carbonyloxyethyl, propionyloxyethyl, bromopropionyloxyethyl, methoxy propionyloxyethyl, chloromethoxypropionyloxyethyl, cyanomethoxypropionyloxyethyl, ethoxypropionyloxyethyl and propionylpropionyloxyethyl,

R is a member selected from the group consisting of methoxy, ethoxy, acetylamino, chloroacetylamino, methoxyacetylamino, ethoxyacetylamino, propyloxyacetylamino, methoxycarbonylamino, ethoxycarbonylamino, propylcarbonylamino, propyloxycarbonylamino, halogenoethoxycarbonylamino, methoxyethoxycarbonylamino, phenyloxycarbonylamino, phenylmethoxycarbonylamino, .propionylamino, halogenopropionylamino, methoxypropionylamino and ethoxypropionylamino.

The following amines are examples of suitable diazo components:

2-amino-3,5-dinitro-1-methylsulphonylbenzene, 2-amino2,5-dinitro- 1 -ethylsulphonylbenzene, 2-amino-3,S-dinitro-l-chl0romethy1sulphonylbenzene, 2-amino-3,5-dinitrol-cyanomethylsulphonylbenezene, 2-amino-3 ,S-dinitro-1-hydroxyethylsulphonylbenzene, 2-amino-3,5-dinitro-1,,8'-chloroethylsulphonylbenzene.

Examples of suitable coupling components are:

S-acetylamino-l-N-(2'-acetoxyethyl)-N-ethylamino-5- methoxybenzene,

5 -acetylamino-1-N- (2-acetoxyethyl) -N-ethylamino-5- ethoxybenzene,

S-acetylamino-Z-ethoxyl-N- 2-acetoxyethyl) -N-pro pylaminobenzene,

S-acetylamino-Z-ethoxyl-N-(2'-acetoxyethyl)-N-methylaminobenzene,

S-acetylamino-Z-ethoxyl-N- (2'- acetoxyethyl N-butylaminobenzene,

S-acetylamino-Z-ethoxy-l-N-ethyl-N- 2'-methoxycarbonylethyl) amin ob enzene,

5-acetylamino-2-ethoxyl-N-ethyl-N- (2'-carbethoxyoxyethyl aminobenzene,

S-acetylamino-Z-ethoxy-l-N-ethyl-n-(3'-acetoxypropyl) aminobenzene-l-N-ethyl-N-(2'acetoxyethyl)amino-3- methoxy-S-propionylaminobenzene,

l-N-ethyl-N- (2-acetoxyethyl amino-Z-methoxy-S-methylbenzene,

l-N-ethyl-N- (2'-acetoxyethyl amino-2,5-dimethoxybenzene,

l-N-ethyl-N- (2'-acetoxyethyl) amino-S- 2'-chloropropionyl) amino-Z-methoxybenzene,

Z-ethoxyl-N-ethyl-N- (2'-acetoxyethyl amino-S- (2' chloroethoxycarbonyl) aminobenzene,

2-ethoxyl-N-ethyl-N-(2-acetoxyethyl) amino-5 carbethoxyaminobenzene,

2-ethoxy-1-N-(2'acetoxyethyl)-N-butylamino-5- carbethoxyaminobenzene.

Generally the coupling reaction is effected in an acid medium, which may be buttered if necessary, and with cooling, for example at temperatures of 0 to 5 C.

The new dyes thus obtained are excellent disperse dyes. It is of special advantage to convert them by known methods into dye preparations before use. This is effected by comminution to an average particle size of about 0.01 to 10 microns or more particularly 0.1 to 5 microns. Comminution can be carried out in the presence of dispersants or fillers. For example, the dried dye can be ground with a dispersant, if necessary in the presence of fillers, or it can be kneaded in paste form with a dispersing agent and subsequently vacuum or jet dried.

After the addition of a suitable volume of water the resulting preparations can be used for dyeing, padding or printing at long or short liquor ratios. For dyeing at long liquor ratios it is general practice to use amounts of up t about 20 grams of dye per litre; for padding, up to about 150 grams or preferably 0.1 to 100 grams per litre; and for printing, up to about 150 grams per kilogram of the print paste. The liquor ratio may vary Within wide limits, e.g., from about 1:3 to 1:200 or preferably 1:3 to 1:80.

The dyes build up excellently from aqueous dispersion on products made of synthetic or semisynthetic hydrophobic organic articles of high molecular weight. They are especially suitable for dyeing, padding or printing filaments, loose fibres and textile materials of linear aromatic polyesters, cellulose diacetate and cellulose triacetate. They can also be used for dyeing synthetic polyamides, polyolefins, acrylonitrile polymerization products and polyvinyl compounds. High quality dyeings are obtained on linear aromatic polyesters, which in the main are polycondensation products of terephthalic acid and glycols, notably ethylene glycol, and are marketed under the registered trade names Terylene, Diiolen, Dacron, etc.

The known dyeing methods are used. Polyester fibres can be exhaustion dyed in the presence of carriers at temperatures of about 80 to 125 C., or in the absence of carriers, under pressure at about 100 to 140 C. These fibres can also be padded or printed with aqueous dispersions of the new dyes and the paddings or prints fixed at about 140 to 230 C. with the aid of water vapour or air. In the optimum temperature range of 180 to 220 C. the dyes diffuse rapidly into polyester fibre and do not then sublime, even when exposed for some length of time to these high temperatures, so that there is no inconvenient contamination of the dyeing and fixing equipment. Cellulose diacetate is dyed preferably in the temperature range of about 65 to 80 C. and cellulose triacetate, at temperatures up to about 115 C. The optimum pH region is 2 to 9 or more particularly 4 to 8.

The normal dispersing agents, preferably those of anionic or nonionic character, can be used, either alone or in mixture. Often about 0.5 gram dispersing agent per litre of the dyeing medium is sufficient, although larger amounts up to about 3 grams per litre can be used. Amounts in excess of 5 grams do not usually offer any further advantage. Known anionic dispersing agents suitable for the process are, for example, the condensation products of naphthalenesulphonic acids and formaldehyde, in particular dinaphthylmethane disulphonates, the esters of sulphonated succinic acid, Turkey red oil, the alkaline salts of the sulphuric acid esters of fatty alcohols, e.g., sodium lauryl sulphate or sodium cetyl sulphate, sulphite cellulose waste liquor and its alkaline salts, soaps, and the alkaline sulphates of the monoglycerides of fatty acids. Examples of known and specially suitable nonionic dispersing agents are the adducts of approximately 3-40 mols of ethylene oxide with alkyl phenols, fatty alcohols or fatty amines, and their neutral sulphuric acid esters.

The normal thickening agents are used for padding and printing, e.g., modified or unmodified natural products such as sodium alginates, British gum, gum Arabic, crystal gum, locust bean gum, gum tragacanth, carboxymethyl cellulose, hydroxyethyl cellulose, starches, or synthetic products, such as polyacrylamides and polyvinyl alcohol.

The dyeings obtained are extremely fast to heat (i.e., thermofixation, sublimation and pleating), gas fumes, cross dyeing, dry cleaning, chlorine, and to wet tests, such as water, washing and perspiration. The dischargeability and reserve of wool and cotton are good. The light fastness is outstanding even in pale shades, which makes the new dyes very suitable as components for the production of fashionable combination shades in pastel depths.

The dyes are stable to boiling and reduction at temperatures up to at least 220 C., showing particularly good stability at to 140 C.; this stability is not adversely affected either 'by the liquor ratio or by the presence of dyeing accelerants.

The blue members of this new group of dyes are suitable for combination with small amounts of red dyes for the production of low-cost navy blue dyeings which are fast to light, washing, perspiration, sublimation, pleating and thermofixation, and also for combination with red and yellow dyes for fast black dyeings. Combination dyeings with yellow dyes shown an even tone-in-tone fade On exposure to light.

In the following examples the parts and percentages are by weight and the temperatures are in degrees centigrade.

EXAMPLE 1 6.9 parts of finely divided sodium nitrite are added slowly with stirring to 120 parts of concentrated sulphuric acid at 60-70. Stirring is continued for 10 minutes at 60, then after cooling to 10 100 parts of glacial acetic acid are added at 1015, followed by 26.1 parts of 2-amino- 3,S-dinitro-l-methylsulphonylbenzene and 100 parts of glacial acetic acid. After stirring for a further 4 hours, the resulting diazonium salt solution is run into a mixture of 33.6 parts of 5 acetylamino-Z-ethoxy-l-N-(2'-acetoxyethyl)-N-butylaminobenzene, 100 parts of glacial acetic acid, 10 parts of aminosulphonic acid and 200 parts of ice. The coupling reaction is brought to completion in acid medium by adjusting the pH to 2.0-2.5 with sodium acetate. The dye forms immediately and settles out. It is filtered off, washed free of acid and dried. It dyes synthetic fibres in greenish blue shades which have excellent fastness properties.

Dyeing instructions 1 A mixture of 7 parts of the dye obtained as described in Example 1, 4 parts of sodium dinaphthylmethanedisulphonate, 4 parts of sodium cetylsulphate and 5 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to give a fine powder. 2 parts of the powder are dispersed in 3000 parts of water containing 3 parts of a 30% solution of a highly sulphonated castor oil and 20 parts of an emulsion of a chlorinated benzene. At 2025 100 parts of a fabric of Dacron (registered trade mark) polyester fibre are entered into the bath, its temperature is raised to 100 in about 30 minutes and the fabric dyed for 1 hour at this temperature. On removal from the bath the fabric is rinsed, soaped for 15 minutes at 70 with a 0.1% solution of an alkylphenylpolyglycol ether, rinsed again and dried. A greenish blue dyeing with excellent fastness properties is obtained.

Dyeing instructions 2 A mixture of 30 parts of the dye obtained as described in Example 1, 40 parts of sodium dinaphthylmethanedisulphonate, 50 parts of sodium cetylsulphate and 50 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to a fine powder. 4 parts of this powder are added to 1000 parts of water at 40-50. Parts of a fabric of Terylene (registered trademark) polyester fibre are entered into the bath, the temperature is increased at a low rate and the fabric dyed for about 1 hour at under pressure. On removal it is rinsed, soaped, rinsed and dried. A greenish blue dyeing having excellent fastness properties is obtained.

Dyeing instructions 3 A mixture of 15 parts of the dye obtained as described in Example 1, 20 parts of sodium dinaphthyhnethanedisulphonate, 25 parts of sodium cetylsulphate and 25 parts of anhydrous sodium sulphate is ground in a ball mill for 48 hours to a fine powder. 5 parts of the powder are added to 4000 parts of water. 100 parts of a secured fabric glycol ether, rinsed again and dried. A greenish blue dyeof Arnel (registered trademark) triacetatc fibre are ing having good fastness properties is obtained.

entered into the bath, the temperature increased slowly The dyes set out in the following table are produced in to 95 100 and the fabric dyed at this temperature for accordance with the procedure of Example 1 from a about 1 hour. On removal it is rinsed, soaped for 15 mindiazotized amine of Formula II and a compound of 1 1 1 2 bonyloxyethyl, (2 methoxypropyDcarbonyloxy- 6. The dye of the formula: ethyl, propionyloxyethyl, bromopropionyloxyethyl, N02 OCHZCH3 methoxypropionyloxyethyl, chloromethoxypropronl /C4Hv yloxyethyl, cyanonmethoxypropionyloxyethyl, leth- I oxypropionyloxyethyl and propionylpropiony oxy- 5 I I CHZCHZO O 0 CH3 y 802C113 NHCOCH;

R is a member selected from the group of radicals 7 The dye of the formula, consisting of methoxy, ethoxy, acetyla'mino, chloroacetylamino, methoxyacetylamino, ethoxyacetylami- ()OHYCHB GRACE: no, propyloxyacetylamino, methoxycarbonylamino, ethoxycarbonylamino, propylcarbonylamino, pro- O2N N=N pyloxycarbonylamino chloroand bromoethoxycar- I i l CHzCHzOCOCI-I; b'onylamino, methoxyethoxycarbonylamino, phenyl- SOZCH; NHGOGH oxycarbonylarnino, phenylmethoxycarbonylamino, 8. The dye of the formula: propionylamino, chloroand br0m0pr-0pi0nylamin0, o, 11 methoxypropionylamino and ethoxypropionylamino. /0H2CH3 2. A disperse dye of the formula ()2N- -N=N N\ I CHzCHzOCOCHa 502C113 NHCOCH; R3 9. The dye of the formula:

N02 OCH; om: N=N N\ I 1 /CHZCH3 I R4 O2N- N=N N 802R: Pia O 'I CHzCHzOCOCHa SOzCH; NHCOCHzCHs h 10. The dye of the formula: W N02 oouzom R is a member selected from the group consisting of I l Y unsubstituted and substituted alkyl, the alkyl having O2N-N=N N r from -1 to 2 carbons, inclusive, and any substituent I \CHQCHQOCOCHQ being selected from the group consisting of chlorine $020113 NHCOCHzOH 9 bmmme, cyano and Y Y 11. The dye of the formula:

R is a member selected from the group consisting of 0 H C methoxy and ethoxy; 3 2 0C 2 H3 CH2CH3 R is a member selected from the group consisting of N methyl, ethyl, propyl and butyl; O2 N R is a member selected from the group consisting of GHZCHZCOOCHB unsubstituted and substituted alkylcarbonyloxyalkyl, SOZCH NHCOCHZOH: alkoxycarbonylalkyl and alkoxycarbonyloxyalkyl, 40 The dye of the formula: each subst-ituent being a member selected from the N02 OCH; group consisting of chlorine and bromine, cyano, CECE alkoxy and alkylcarbonyl, and each alkyl and each OzN- N=N N alkoxy having at most four carbon atoms; and r l \CHZCHGOOOCHa R is a member selected from the group consisting $020113 NHCOOHzCHa of alkyl, alkoxy, and substituted and unsubstituted alkylcarbonylamino, alkoxycarbonylamino, phen- References Clted alkoxycarbonylamino and phenoxycarbonylamino, I UNITED STATES PATENTS each substituent being a member selected from the 2,111,300 3/1938 Senn 260M207 group consisting of chlorine and bromine and 3,268,507 8/1966 Kruckenberg L fi f jgg fggg and each anmy havmg 3,342,803 9/1967 Artz et a1. 260-207 St; A 1dye alicqrding to claim 1 wherein R is an alkyl- CHARLES PARKER, Primary Examiner car ony oxya y. y

4. A dye according to claim 1 wherein R is an alkoxy- PAPUGA Ass'stam Exammer' carbonylalkyl.

US. Cl X.R.

5. A dye according to claim 1 wherein R is an alkoxycarbonyloxyalkyl.

P/35"" Um'ruio s'm'ms PATENT 0mm CEliTIP-EQCATE OF CORRECTION Patent No I 3 f28,622 Dated February 18, l969 Invm1t01"(5) Ruedi Altermatt and Curt Mueller It is certified that error appears in the above-identified patent and that said LetLers Patent are hereby corrected as shown below:

Column 1, line 39, "carbonyloxyalkyl; and" should read -carbonyloxyalkyl and-- line 65, "(IV" should read --(IV)--. Column 2, line 27, "2-am1no2" should read 2-amino3--; line 32, "l,B' "should read -l-B'-, line 41, "ethoxyl" should read --ethoxy-l-; line 49, "(3'-acetoxypropy1)" should read -(3'-acetoxypropyl)- line 50, "(Z'acetoxyethyl)" should read (2'-acetoxyethyl)-; line 58, "(2' should read --(2'- line 62, "(2' acetoxyethyl)" should read (2'aeetoxyethyl)-. Column 3, line 26, "Diiolen" should read --Diolen-; line 63, "products" should read -products,-. Column 5, Example 3, "OCH CH should read -0CH CH second example "3" should read -4--; example "4" should read --5--; in Example 4, "C li should read C H In each example 5, 6, 7 and 8, "0Cl1 CH should read -0CH Example 5, "C H should read -CH xample ll, "-NHCOCH CI3 should read I?H5OCH CH Example 11,

"Do should read -Do.--; Example 17, "CH should read C H Example 32, "C H should read -C H Example 58, "OC should read -0CH Column 10, upper righ? portion of formula for Example 22,

"OCH shoul read --(|)CH CH line 60, "cosnisting" should read -consist ing. Column 12, claim 11, "NHC0CH2CH3" should read -NHCOCH3-.

SIGNED AND SEALED APR281970 (SEAL .Attest:

L Edward M- Fletcher, If. WILL urt-[ER JR. J

Auesting Officer Commissionerof Patents 

